Process of producing aldehydes using a catalyst including a group viii metal and phosphorus

ABSTRACT

In the production of aldehydes by reaction of carbon monoxide, hydrogen, and olefinically unsaturated compounds, utilizing a catalyst based on a Group VIII metal, e.g. cobalt, which catalyst includes as an additive, a phosphorus compound, the performance of the catalyst is improved, particularly in that high yields are obtained without the increase of reaction time commonly occasioned by use of a phosphorus compound, by using a phosphorus compound of the formula, for example:   WHEREIN R1, R2, R3, R4, R5 and R6 are the same or different nonsubstituted or substituted aliphatic, cycloaliphatic, heterocyclic or aromatic radicals, A1 and A2 represent similar or different bridge atoms selected from the group comprising oxygen, sulfur, nitrogen and phosphorus and n is an integer having a value of 0 or 1 and even 2 if the bridge atom is sulfur, nitrogen or phosphorus.

United States Patent Falbe et al.

[54] PROCESS OF PRODUCING ALDEHYDES USING A CATALYST INCLUDING A GROUPVIII METAL AND PHOSPHORUS [72] Inventors: Jurgen Falbe, Dinslaken; HansTummes, Oberhausen-Sterkrade- Nord; Jurgen Weber, Oberhausen- Holten,all of Germany [73] Assignee: Ruhrchemie Aktiengesellschaft,

Oberhausen-l-lolten, Germany [22] Filed: Nov. 1, 1968 [21] Appl. No.:772,612

[30] Foreign Application Priority Data Nov. 7, I967 Germany ..P 16 68622.9 Sept. 2, 1968 Austria ..A 8496/68 [52] U.S. Cl. ..260/604 HF,260/927 R [51] Int. Cl. ..C07c 45/08, C07c 45/10, C07f 9/28 [58] Fieldof Search ..260/604 HF, 927

[56] References Cited UNITED STATES PATENTS 3,351,666 11/1967Mertzweiller et al.,.260/604 HF 3,496,204 2/1970 Morris et al ..260/604HF X [is] -3,68l,465

[451 Aug. 1, 1972 Primary ExaminerJoseph Rebold AssistantExaminer-Richard L. Raymond Attorney-Burgess, Dinklage & Sprung [5 7]ABSTRACT COORz wherein R R R R R and R are the same or differentnon-substituted or substituted aliphatic, cycloaliphatic, heterocyclicor aromatic radicals, A and A represent similar or different bridgeatoms selected from the group comprising oxygen, sulfur, nitrogen andphosphorus and n is an integer having a value of 0 or 1 and even 2 ifthe bridge atom is sulfur, nitrogen or phosphorus.

26 Claims, 1 Drawing Figure PATETEDW 1 I97? 3.681. 465

Ju gew 5/1 ,grmwvw:

BACKGROUND OF THE INVENTION The production of aldehydes by the additionof carbon monoxide and hydrogen to olefinically unsaturated compounds inthe presence of a catalyst, whereby aldehydes having one more carbonatom than the olefinic compound are obtained, is well known in the art(see J. Falbe, Synthesen mit Kohlenmonoxyd, 1967, page 3 ff). Thisreaction, the so-called oxosynthesis, is industrially achieved with sometypes of catalysts, among which cobalt is preferred. It can be employedin different forms (see Falbe, l.c., page 13 ff). The oxosynthesis canalso be carried out with other metals, for instance rhodium, rutheniumor iron, as is well known in the art (see Falbe, l.c., page 21 ff).

Under the reaction conditions of the oxo-synthesis using cobalt in anyform, cobalt carbonyl hydride, which is the active catalyst, is formed.The oxo process is generally conducted at temperatures between 100 and200 C and total pressures from 100 to 400 atm.

In addition to the aldehydes, which are obtained as the primaryproducts, significant amounts of byproducts are formed, as for instancealcohols, resulting from the hydrogenation of the said aldehydes.Furtheron, formic acid esters and higher boiling condensation productsof the primaryly formed aldehydes are formed besides other substances.Some hydrogenation of the olefinic compounds, used as startingmaterials, to corresponding saturated reaction products also takesplace.

Since at the hydroformylation of most olefinic starting material(insofar as they are not symmetric and not isomerizable by migration ofthe double linkage, as for instance ethylene and cyclopentene),isomerizations of the complexes intermediaryly formed from therespective olefinic compound and the carbonyl occur under the prevailingreaction conditions, mixtures of several isomeric reaction products aregenerally obtained.

One embodiment of the 0x0 synthesis is known,

whereby complexes from distinct phosphines, carbon monoxide andtransition metals, as for instance cobalt, rhodium and so on, areemployed as catalysts (see DAS l 186 455 and DAS l 212 953). With thisknown method, the reaction shall be conducted under pressures of 35 to150 atm and at temperatures from 160 to 200 C. It is said, that hereby ahigher ratio of normal to branched aldehydes and/or normal to branchedalcohols is obtained from normal olefines than can be obtained withmetal catalysts, especially cobalt catalysts, without addition ofphosphines. Furtheron, it has been stated, that the said process resultsin the hydrogenation of remarkable amounts of the primarily formedaldehydes to alcohols. The undesired formation of higher boilingcondensation products is reduced in comparison to processes operatingwith cobalt catalysts without added phosphorus compounds.

A disadvantage inherent in this embodiment of the 0x0 synthesis is, thatgenerally more than 10 percent of the olefinic compounds used asstarting materials are hydrogenated to saturated hydrogenation productsand that a significant decrease of the reaction velocity must betolerated. Owing hereto, larger sized reaction vessels are necessary, ifequal throughputs as can be obtained with phosphine-free catalysts shallbe attained.

It is also known to employ phosphites instead of phosphines asadditional catalysts together with cobalt catalysts (see DAS l 146 486and DAS l 230 010). With the addition of phosphites, the hydrogenationof aldehydes primarily formed to corresponding alcohols shall besignificantly reduced, but the added phosphites also lead to a decreaseof the reaction velocity of the synthesis in comparison with the use ofcobalt catalysts containing no phosphine or phosphit additives.

THE INVENTION It is an object of the invention, to convert olefins toaldehydes with high yields in presence of 0x0 synthesis catalystscontaining an addition of phosphorus compounds whereby a decrease of thereaction velocity is substantially avoided.

It has now been found, that the production of aldehydes by reaction ofolefinic compounds with carbon monoxide and hydrogen at elevatedtemperature and elevated pressure in presence of catalysts containing ametal of Group VIII of the periodic system (i.e. a transition metal) canbe formed with excellent results, if a compound is added to the catalystwhich has been prepared by reaction of malonic acid diesters withcompounds of trivalent phosphorus, which contain directly linked to thephosphorus atom at least two halogen atoms, e.g. chloro, capable ofreacting with activated hydrogen atoms. The phosphorus compound can havetwo halogen atoms, e.g. chloro, and as a third substituent an organicgroup, e.g. an aromatic or alkyl group connected directly or through-O-, -S, N- or -P to the phosphorus.

Especially well suited as catalyst additives are compounds of thegeneral formula R40 I i) 11-35 wherein R R R R R and R are the same ordifferent non-substituted or substituted aliphatic, cycloaliphatic,heterocyclic or aromatic radicals, A, and A represent similar ordifferent bridge atoms selected from the group comprising oxygen,sulfur,.

nitrogen and phosphorus and n is an integer having a value of 0 or 1 andeven 2 if the bridge atom is sulfur, nitrogen or phosphorus. Moreparticularly the groups R R R and R each can be alkyl, especially loweralkyl (up to four carbon atoms); R and R each can be alkyl or a phenylgroup of the formula are used as catalyst additives. Herein R R and Rcan have the values assigned thereto above.

Advantageous results are further obtained, if compounds of the generalformula are used as catalyst additives. In the said formula R R and R,can have the values assigned thereto above.

Under the conditions of the 0x0 synthesis the catalytic compoundscontaining a transition metal of Group VIII of the periodic table areconverted to corresponding carbonyl compounds, which form complexes withthe phosphorus compounds added according to the invention; the resultingcomplexes are more resistant to high temperature and less volatile incomparison to simple carbonyl compounds.

The catalysts used in the process of the invention effect a pronouncedselectivety for the formation of aldehydes. Hydrogenation of theolefinic starting materials to corresponding saturated compounds as wellas hydrogenation of the resulting aldehydes to alcohols is substantiallysuppressed. A further valuable aspect of the process according to theinvention resides in its ability to decrease significantly the formationof other undesired side products, as for instance formic acid esters, incomparison with conventional processes. A

supplemental increase of the aldehyde yield, which however in certaininstances is connected with a decrease of the reaction velocity, can beattained by addition of alkali hydroxides to the catalyst system.Addition of tertiary amines, if desired together with alkali hydroxide,can also effect a further increase of the aldehyde yield.

The process according to the invention has significant advantages incomparison to known processes working with conventional catalysts as forinstance cobalt carbonyl compounds in absence of additives due to thefact, that the phosphorus compounds used as catalyst additives don'tremarkably impair the velocity of the hydroformylation reaction. Incontrast hereto, the hitherto used phosphorus containing catalystadditives cause a remarkable decrease of the reaction velocity resultingin a decrease of the yield of valuable products obtainable per unit oftime in reaction vessels of identical size.

Outstanding results are obtained, if the phosphorus containing compoundsused according to the process of the invention are applied together withcatalysts containing cobalt, rhodium, ruthenium or iron.

Several individual compounds, which are typical examples for suitablecatalyst additives are hereinafter listed.

TABLE 1 1. l-ethoxy-l ,2-diphenyl-[ l ,Z-diphosphacyclopenten-( 5)-one-(4 tricarboxylic acid-( 3 ,3 ,5 triethylester 2. l-ethoxyl ,2-di-(4-chloro-phenyl)-[ l ,2-

diphosphacyclopenten-( 5 )-one-(4)]-tricarboxylic acid-( 3 ,3 ,5)-triethylester 3. l-ethoxyl ,2-di-(4'-methyl-phenyl)-[ l ,2-diphosphacyclopenten-( 5 )-one-(4) ]-tricarboxylic acid-( 3,3 ,5 )-triethylester 4. l-ethoxy-l ,2-di-( 4'-dimethylamino-phenyl)-[ l ,2-diphosphacyclopenten-( 5 )-one-( 4) l-tricarboxylic acid-( 3 ,3,5)-triethylester S. l-ethoxy-l,2-di-(4'-fluoro-phenyl)-[ 1,2-diphosphacyclopenten-( 5 )-one-(4 -tricarboxylic acid-( 3 ,3 ,5)-triethylester 6. l-ethoxyl ,2-di( 2'-tert,-butyl-phenoxy)-[ l ,2-diphosphacyclopenten-( 5 )-one-(4) ]-tricarboxylic acid-( 3,3 ,5)-triethylester 7. l-ethoxyl ,2-di-( 2',5 '-dimethyl-phenyl)-[ 1 ,2-diphosphacyclopenten-( 5 )-one-( 4) ]-tricarboxylic acid-( 3 ,3 ,5)triethylester 8. l-ethoxy-l,Z-di-(N-methyl-anilino)-}1,2-diphosphacyclopenten-( 5 )-one-( 4 -tricarboxylic acid-(3,3,5)-triethylester 9. l-methoxyl ,2-diphenyl-[ l ,2-diphosphacyclopenten(5)-one-(4)]-tricarboxylic acid-)3,3,5 trimethylester 10.l-tert.-butoxy-l ,2-diphenyl-[ 1 ,2-diphosphacyclopenten-( 5 )-one-( 4tricarboxylic acid-( 3 ,3,5 )-tritert.-butylester 1 l. l -tert.-butoxy-l,2-di-(4'-dimethylamino-phenyl H l ,Z-di-phosphacyclopenten-( 5 )-one-(4) ]-tricarboxylic acid-( 3 ,3 ,5 )tri-tert.-butylester 12. l-ethoxy-l,2-di-n-butyl-[ l,2-diphosphacyclopenten-( 5 )-one-(4 l-tricarboxylicacid-( 3 ,3 ,5 triethylester The hereinbefore listed derivatives of1,2-diphosphacyclopenten-(5)-one-(4) can for instance be prepared byreaction of malonic acid diesters with compounds of trivalent phosphorushaving directly linked to the phosphorus atom at least two halogen atomscapable of reacting with activated hydrogen atoms, whereby hydrogenchloride evolved during the reaction is continuously removed from thereaction mixture by addition of a base, as for instance a tertiaryamine. The substituent (A )n P or (A )n R of the first of the abovestructural formulas can be the third substituent of the trivalentphosphorus compound. The course of the reaction will be apparent fromthe foregoing structural formula. The conversion between the reactantsproceeds at ambient or slightly increased temperature, it isadvantageously carried out at 40 to 60 C. In special instances, as forexample with steric hindered reactants, higher temperatures may berequired. Preparation of compound 1 of Table l is disclosed in copendingapplication Ser. No. 765,687 filed Oct. 7, 1968 of Gunter Bergerhoff,Bela Tihanyi, Jurgen Falbe and J urgen Weber, for Phenyl-SubstitutedPhosphorus Compound And Process For Its Preparation. The followingexample appears in said copending application.

EXAIVKPLE:

17.9 g phenyl-phosphine dichloride (0.1 mole) and 16.0 g malonic aciddiethylester (0.1 mole) are dissolved in 250 ml benzene and heated to 50C under a nitrogen atmosphere. 20.2 g (0.2 mole) triethylamine,dissolved in 100 ml benzene are added dropwise under stirring.Precipitated triethylamine hydrochloride is separated by filtration andwashed with benzene. The benzene filtrate together with the washingsolution is concentrated to about one third of its volume by evaporationat 40 to 50 C under water-jet vacuum. Thereby a colorless crystal sludgeis precipitated which is sucked off and washed with ether. This productcan be purified by recrystallization from benzene followed by washingwith alcohol and ether. The pure compound has a melting point of 1 14 C.The entire yield amounts to 70 to 80 percent by theory.

The catalysts are applied in amounts generally used in oxo-synthesisprocesses. Cobalt and ruthenium for example are used in concentrationsof about 0.01 to 5 percent by weight, preferably 0.1 to 1.5percent byweight of metal related to the olefinic compound to be converted.Rhodium is generally applied in a concentration of 0.00001 to 0.5percent by weight, preferably 0.001 to 0.1 percent by weight of Rh,related to the amount of the olefinic compound to be reacted. The atomicratio of metal to phosphorus generally ranges between 1:05 to 1:10,preferably 120.5 to 1:3. If desired, metal and phosphorus may be appliedin an atomic ratio, which is higher or lower than the hereinbeforestated values.

The process according to the invention is advantageously carried out atpressures in the range from 50 to 400 Atm, preferably from 150 to 300Atm, a molar ratio of carbon monoxide to hydrogen from 1:5 to 5:1,preferably 1:1 is maintained. The reaction temperature ranges from 70 to250 C, preferably from 90 to 180 C. In this regard it must beconsidered, that the aldehyde yield is temperature dependent. The amountof aldehydes in the reaction product related to the olefinic startingmaterial increases with decreasing reaction temperature whilesimultaneously a decrease of the reaction velocity is observed. It isessential to effect the reaction at low temperatures, if normal olefinsshall be converted to unbranched reaction products.

The reaction of olefins with carbon monoxide and hydrogen according tothe process of the invention may be effected in presence as well as inabsence of inert solvents or diluents. Suitable solvents are forinstance aliphatic, cycloaliphatic or aromatic hydrocarbons, ethers,esters, ketones or the reaction product itself or fractions thereof asfor example higher boiling residues, preferred solvents are hexane,octane, cyclohexane, benzene, toluene, xylene, diphenylether,tetrahydrofurane or mixtures of those substances.

The reaction may be conducted discontinuously or preferablycontinuously. Due to the outstanding then mal stability and the lowvolatility of the complexes formed in the reaction mixture from metalcarbonyl compounds and the phosphorus containing compounds, the reactionproduct can be separated from the catalyst in simple manner. Theseparation is performed in such a manner, that the catalyst remains inthe sump phase and can be recirculated in liquid phase, if desired afterreplenishment of small losses by fresh catalyst.

The following examples 1-18 illustrate the discontinuoushydroformylation of olefins with the process according to the invention;examples 1 to 17 being concemed with conversions in presence of cobaltcatalysts, while example 18 illustrates the use of a rhodium catalyst.Examples 19 and 20 describe continuous hydroformylation processes.

EXAMPLES l to 17 A 2.1 1 stainless steel autoclave (V4A) equipped with alifting magnet stirrer was charged with 300 g benzene, 3.45 gdicobaltoctacarbonyl respectively and, except in comparison test 1,individual phosphorus containing additional catalysts noted in table 1as well as KOl-l if desired were added. The phosphorus compound wasthereby employed in an amount corresponding to an atomic ratio Co:P=1:1.1.

The autoclave contents were heated up to the respective temperaturesnoted in table 1 in presence of CO and H in a ratio of 1: 1, and under apressure of 250 atm., g hexene-(l) were introduced into the autoclavewith the aid of a pressure dosing pump. The synthesis gas consumedduring the course of the reaction was continuously replenished by meansof an automatic pressure regulating equipment, so that pressure drop inthe autoclave was prevented. The course of the reaction was controlledby regular sampling and gas chromatographic analysis. After completionof the reaction, the autoclave was discharged and the composition of thereaction product was determined by vacuum distillation andgaschromatographic analysis.

The test results are summarized in the attached table, wherein thephosphorus compounds employed as catalyst additives are characterized bynumerals corresponding with the numeration of the individual compoundslisted as typical examples in Table 1.

TABLE2 Hydroformylation of Hexene- 1) Reaction Co- 0.8% by weightconditions: pressure :250 atm. concenrelated to oletration finicstarting material molar ration atomic H :CO 1:1 ration Co:P :1'.l.1solvent benzene weight ratio solvent :olefin 22:1

Test Catalyst Temp yields: from 100g No. C hexene-( 1) are obtained (ing) aldealkoforparafhigher reaction hydes hols mic fins boilitime (inacid ng coh) up to estnsti- 95% coners tuents version 1 Co (CO) 74.225.0 11.1 2.5 23.0 1 2 Co,(CO)

Triphenylphosphite 170 115.8 6.8 4.1 2.2 7.3 3 3 Co (CO)Tributylphosphine 170 63.8 43.8 16.2 8.2 5.1 2 4 C0 (CQ)a+ P-compoundl170 123.4 2.6 1.3 2.3 5.9 1.5 5 Co (CO) Tributylphosphine+ 1 mol KOH/gramatomP 170 61.1 29.5 33.1 10.2 6.0 5 6 Co (CO) P-compound 1 1 mol KOHgramatomP 170 126.7 0.9 2.0 4.0 3

P-compound l 2 mol KOl-l lgramatomP 1701296 1.4 0.8 1.4 2.3 3

P-compound3 170 120.8 3.1 2.9 2.3 6.5 1.5

EXAMPLE 18 A 4 1 stainless steel autoclave (V4A) equipped with a liftingmagnet stirrer was charged with 800 g toluene, 0.4 g rhodium (in form ofrhodium-Z-ethylhexanoate) and 0.2 gl-ethoxy-l,2-diphenyl-[1,2-diphosphacyclopenten-( 5 )-one-(4)]-tricarboxylic acid-( 3 ,3,5 triethylester and the autoclave contentswere heated in presence of CO and H in a ratio of 1:1 at a pressure of250 at to 170 C. 400 g hexene-l were introduced into the autoclave witha pressure dosing pump. The synthesis gas consumed during the course ofthe reaction was continuously replenished by means of an automaticpressure regulating equipment, so that pressure drop in the autoclavewas prevented. The course of the reaction was controlled by regularsampling and gas chromatographic analysis. After a conversion time oftwo hours the autoclave was discharged and the composition of thereaction product was determined by vacuum distillation andgas-chromatographic analysis. More than 95 percent of the convertedhexene-( l) were present as nand i-heptanal respectively.

CONTINUOUS PROCESS ln examples l9 and 20, the continuous performance ofthe hydroformylation reaction with the process according to theinvention is illustrated, whereby the hereinafter described apparatus,shown in the attached drawing, was used.

To a reactor 4, olefin, synthesis gas (CO to E l: 1) and catalyst wereintroduced through conduits l, 2 and 3. The reaction products weredischarged from the reaction vessel through conduit 5 and introducedinto sump area 7 of a distillation column 6. The components of thereaction product being distilled oil from the column are led via cooler8 to a separator 9 and may be recirculated by means of a pump 10 asreflux to head 11 of column 6 or discharged at 12. High boilingconstituents of the reaction product containing the hydroformylationcatalyst remain in the sump area 7 of column 6. This catalyst containingthe remainder is recirculated to reactor 4 by means of pump 13. Freshcatalyst is introduced via conduit 16. Residual gas from distillationcolumn 6 is expanded through conduit 17 or is recirculated viacirculating pump 14 to sump area 7. During the course of the testreaction the liquid level in the sump space is maintained constant bycontinuous removal of sump product via conduit 15.

EXAMPLE 19 In reactor 4, 3.5 kg commercially available propylene perhour (corresponding to an average residence time of 45 minutes) arereacted with carbon moxide and hydrogen (ratio 1:1) in presence ofdicobaltoctacarbonyl and l-ethoxy-l, 2-diphenyl-[ 1,2-diphosphacyclopenten-( 5 )-one-( 4) ]-tricarboxylic acid-(3,3,5)-triethylester at 160 C and 240 Atm. pressure. The atomic ratio ofcobalt to phosphorus in the catalyst system amounted to 1:1.1. Thecatalyst is dissolved in higher boiling components of the reactionproduct (concentration 4.1 g Cell) and is recirculated in an amount of91 solution/h. The necessary replenishment with fresh catalyst amountsto 0.03 weight percent Co related to the propylene charged. Theresulting raw hydroformylation product was fractionated in column 6 at abottom temperature of 156 C, a distillation pressure of 10 Atm. and agas recycle of 13 Nm. As reaction product 5 kg/h of a distillate of thefollowing composition was obtained.

aldehydes 90.8% formic acid esters 0.4% alcohols 4.0% higher boilingcomponents 4.8%

EXAMPLE 20 1.0 kg commercially available propylene were introduced perhour into reactor 4 and reacted with carbon monoxide and hydrogen (ratio1:1) in presence of dicobaltoctacarbonyl and 1-ethoxy-, l ,2-di-( 4dimethyl-aminophenyl)-[ 1 ,Z-diphosphacyclopenten- (5 )-one-( 4-tricarboxylic acid-( 3 ,3 ,5 )-triethylester at C and 250 Atm.pressure. The atomic ratio of cobalt. and phosphorus in the catalystsystem amounted to 1:1. The catalyst is dissolved in higher boilingcomponents of the reaction product (concentration 4.4 g Co/l) and wasrecirculated in an amount of 12.5 1 solution/h. The necessaryreplenishment with fresh catalyst amounted to 0.007 weight percent Co,related to the propylene charged. The processing of the rawhydroformylation product was performed with the procedure described inExample 19, except that a gas recirculation of 4 Nm /h was maintained.As reaction product about 1.5 kg/h of a distillate of the followingcomposition was obtained.

aldehydes 9 1 6% formic acid esters 1.0% alcohols 3.1% Higher boilingcomponents 4.3%

What is claimed is:

1. In a process of producing aldehydes by reaction of olefins withcarbon monoxide and hydrogen at elevated temperature and elevatedpressure in the presence of a metal of Group VIII of the periodic systemas catalyst for the reaction, the improvement which comprises employingsaid catalyst in combination with the reaction product of malonic aciddiester with trivalent phosphorus compound having two halogen atomslinked directly to phosphorus, and has a third substituent directlylinked to the phosphorus:

wherein R is alkyl or wherein R is hydrogen, halo, alkyl, or amino, A isoxygen or nitrogen, and n is or 1.

2. Process according to claim 1, wherein R, is in the para position andis hydrogen, chloro, alkyl, or dialkylamino and the malonic acid diesteris a di-lower alkyl ester.

3. Process according to claim 2, wherein n is 0.

4. In a process of producing aldehydes by reaction of olefin with carbonmonoxide and hydrogen at elevated temperature and elevated pressure inpresence of a Group VIII metal selected from the group consisting ofcobalt, rhodium and ruthenium as catalyst for the reaction, theimprovement which comprises employing said catalyst in combination withderivatives of the compound l,2-diphosphacyclopenten-()-one-(4) of theformula:

0 o o R,

123000-05 2P(A2)n-Ro wherein each R R R and R is lower alkyl; each R andR is lower alkyl or a phenyl group of the formula:

wherein each R and R is hydrogen, halo, lower alkyl, amino, loweralkyl-amino or di-lower alkylamino; each A and A is oxygen, imido orlower alkyl substituted imido, and n is 0 or 1.

5. Process according to claim 4, in which said compound is of theformulas:

wherein R R and R represent similar or different or substitutedaliphatic, or aromatic radicals.

6. Process according to claim 4, in which said compound is of theformula:

COORi O:UC

wherein R and R represent similar or different, aliphatic, or aromaticradicals.

7. Process according to claim 1, wherein said compound is l-ethoxy-l,2-diphenyl-[ 1,2-diphosphacyclopenten-(S )-one-(4 ]-tricarboxylicacid-( 3,3,5 triethylester.

. 8. Process according to claim 1, wherein said compound is l-ethoxyl,2-di-(4'-chloro-phenyl)-[ l ,2- diphosphacyclopenten-( 5 )-one-( 4]-tricarboxylic acid-(3,3,5 )-triethylester.

9. Process according to claim 1, wherein said compound is l-ethoxyl,2-di-(4-methyl-phenyl)-[ l ,2- diphos'phacyclopenten-( 5 )-one-(4]-tricarboxylic acid-( 3,3 ,5 )-triethylester.

10. Process according to claim 1, wherein said compound is l-ethoxy-l,2-di-(4-dimethylamino-phenyl)- l,2-diphosphacyclopenten-( 5 )-one-( 4)]-tricarboxylic acid-(3,3,5 )-triethylester.

11. Process according to claim 1, wherein said compound is l-ethoxy l,2-di-(4-fluoro-phenyl)-[ 1 ,2- diphosphacyclopenten-( 5 )-one-( 4)]-tricarboxylic acid-( 3,3 ,5 )-triethylester.

12. Process according to claim 1, wherein said compound is l-ethoxyl,2-di-( 2'-tert.-butyl-phenoxy)-[ l ,2- diphosphacyclopenten-( 5 )-one-()-one-(4 ]-tricarboxylic acid-( 3,3,5 )triethylester.

13. Process according to claim 1, wherein said compound is l-ethoxy- 1,2-di-( 2' ,5 '-dimethyl-phenyl)-[ 1 ,2- diphosphacyclopenten-( 5)-one-(4 ]-tricarboxylic acid-( 3 ,3 ,5 )-triethylester.

14. Process according to claim 1, wherein said compound isl-ethoxy-l,2-di-(N-methyl-anilino)-[1,2-diphosphacyclopenten-(5)-one-(4)]-tricarboxylic acid-( 3,3 ,5)-triethylester.

15. Process according to claim 1, wherein said compound is l-methoxyl ,2diphenyl-[ l ,Z-diphosphacyclopenten-(S )-one-(4)]-tricarboxylic acid-(3,3,5 trimethylester.

16. Process according to claim 1, wherein said compound isl-tert.-butoxy-l ,2-diphenyl-[ l,2-diphosphacyclopenten-( 5 )-one-(4)]-tricarboxylic acid-( 3 ,3,5 )tritert.-butylester.

17. Process according to claim 1, wherein said compound isl-tert.-butoxyl ,2-di-(4'dimethylamino-phenyl)-[l,2-diphosphacyclopenten-(5 )-one-(4)]-tricarboxylic acid-( 3,3,5)-tri-tert.-butylester.

18. Process according to claim 1, wherein said compound is l-ethoxy-l,2-di-n-butyl-[ l ,2-diphosphacyclopenten-( 5 )-one-( 4 ]-tricarboxylicacid-( 3 ,3 ,5 triethylester.

19. Process according to claim 1, wherein said catalyst includesalkalihydroxide.

20. Process according to claim 1, wherein said catalyst includes atleast one tertiary amine.

21. Process according to claim 20, said tertiary amine beingtriethylamine.

22. Process according to claim 1, wherein cobalt is the Group VIIImetal.

I 1 I2 23. Process according to claim 1, wherein rhodium is a. thetemperature is about 70 to 250 C, the Group VIII metal. b. the pressureis about 50 to 400 mm,

24. Process according to claim 1, wherein ruthenium the a C ratio o Sa dGrOup III metal to is the Group VIII metal. phosphorus is 1:05 to 1:10,

25. Process according to claim l,whereinanatomic 5 said Group vm metalis cobalt rhodium or ratio of Group VIII metal to phosphorus of 1:05 to1:10 is maintained.

26. Process according to claim 4, wherein:

ruthenium or.

(YER;

ALlgLISC l. 1972 Dated Patent No.

lnventor(s) t m t m M m e h a i e f b C M t n m c m w H fl 5 '0 e s v ad 0 O n e b n t a n a a O t C C a 4 .h C l \l t r u S w r m e m w r n o1 u a f m w R K c a c e O O 5 a D e r h 0 O R 5 a W m t C C c 8 e R5 .ma 8 3 2 a 3 r r o a n l a 1P CI 6 w t h d n L m c 4 5 e t t CIIIHIC 01h5:. v m m 0 R 6 t H 1 2 i 2 s O C & t l m 5 O S i u l O 4 b m u f t 1 6U l i c S R S S a t L e l I n 6 r C i .1 mb a l l I a S S J 9 7 0 .1 t 39 l t a I1 0 o o a t 1 m m W O J m C C a C01. 12, line 6, (Claim 26 line7) cancel "or".

Signed and sealed fiais 15th day' of May 1973 (SEAL) Attests EDWARDMQFLETCHER JRQ ROBERT GQTTSCHALK Attesting Gffiger Commissioner ofPatents

2. Process according to claim 1, wherein R7 is in the para position andis hydrogen, chloro, alkyl, or dialkylamino and the malonic acid diesteris a di-lower alkyl ester.
 3. Process according to claim 2, wherein n is0.
 4. In a process of producing aldehydes by reaction of olefin withcarbon monoxide and hydrogen at elevated temperature and elevatedpressure in presence of a Group VIII metal selected from the groupconsisting of cobalt, rhodium and ruthenium as catalyst for thereaction, the improvement which comprises employing said catalyst incombination with derivatives of the compound1,2-diphosphacyclopenten-(5)-one-(4) of the formula:
 5. Processaccording to claim 4, in which said compound is of the formulas: 6.Process according to claim 4, in which said compound is of the formula:7. Process according to claim 1, wherein said compound is1-ethoxy-1,2-diphenyl-(1,2-diphosphacyclopenten-(5)-one-(4))-tricarboxylicacid-(3,3,5)-triethylester.
 8. Process according to claim 1, whereinsaid compound is1-ethoxy-1,2-di-(4''-chloro-phenyl)-(1,2-diphosphacyclopenten-(5)-one-(4))-tricarboxylic acid-(3,3,5)-triethylester.
 9. Process according to claim1, wherein said compound is1-ethoxy-1,2-di-(4''-methyl-phenyl)-(1,2-diphosphacyclopenten-(5)-one-(4))-tricarboxylic acid-(3,3,5)-triethylester.
 10. Process according toclaim 1, wherein said compound is1-ethoxy-1,2-di-(4''-dimethylamino-phenyl)-(1,2-diphosphacyclopenten-(5)-one-(4))-tricarboxylic acid-(3,3,5)-triethylester.
 11. Process according toclaim 1, wherein said compound is1-ethoxy-1,2-di-(4''-fluoro-phenyl)-(1,2-diphosphacyclopenten-(5)-one-(4))-tricarboxylic acid-(3,3,5)-triethylester.
 12. Process according toclaim 1, wherein said compound is1-ethoxy-1,2-di-(2''-tert.-butyl-phenoxy)-(1,2-diphosphacyclopenten-(5)-one-()-one-(4))-tricarboxylic acid-(3,3,5)triethylester.
 13. Processaccording to claim 1, wherein said compound is1-ethoxy-1,2-di-(2'',5''-dimethyl-phenyl)-(1,2-diphosphacyclopenten-(5)-one-(4))-tricarboxylic acid-(3,3,5)-triethylester.
 14. Process according toclaim 1, wherein said compound is1-ethoxy-1,2-di-(N-methyl-anilino)-(1,2-diphosphacyclopenten-(5)-one-(4))-tricarboxylic acid-(3,3,5)-triethylester.
 15. Process according toclaim 1, wherein said compound is1-methoxy-1,2-diphenyl-(1,2-diphosphacyclopenten-(5)-one-(4))-tricarboxylicacid-(3,3,5)-trimethylester.
 16. Process according to claim 1, whereinsaid compound is1-tert.-butoxy-1,2-diphenyl-(1,2-diphosphacyclopenten-(5)-one-(4))-tricarboxylic acid-(3,3,5)tri-tert.-butylester.
 17. Process accordingto claim 1, wherein said compound is1-tert.-butoxy-1,2-di-(4''dimethylamino-phenyl)-(1,2-diphosphacyclopenten-(5)-one-(4))-tricarboxylicacid-(3,3,5)-tri-tert.-butylester.
 18. Process according to claim 1,wherein said compound is1-ethoxy-1,2-di-n-butyl-(1,2-diphosphacyclopenten-(5)-one-(4))-tricarboxylicacid-(3,3,5)-triethylester.
 19. Process according to claim 1, whereinsaid catalyst includes alkalihydroxide.
 20. Process according to claim1, wherein said catalyst includes at least one tertiary amine. 21.Process according to claim 20, said tertiary amine being triethylamine.22. Process according to claim 1, wherein cobalt is the Group VIIImetal.
 23. Process according to claim 1, wherein rhodium is the GroupVIII metal.
 24. Process according to claim 1, wherein ruthenium is theGroup VIII metal.
 25. Process according to claim 1, wherein an atomicratio of Group VIII metal to phosphorus of 1:0.5 to 1:10 is maintained.26. Process according to claim 4, wherein: a. the temperature is about70* to 250* C, b. the pressure is about 50 to 400 atm., c. the atomicratio of said Group VIII metal to phosphorus is 1: 0.5 to 1:10, d. saidGroup VIII metal is cobalt, rhodium, or ruthenium or.